CN112158923A - Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode - Google Patents
Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode Download PDFInfo
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- CN112158923A CN112158923A CN202010974290.5A CN202010974290A CN112158923A CN 112158923 A CN112158923 A CN 112158923A CN 202010974290 A CN202010974290 A CN 202010974290A CN 112158923 A CN112158923 A CN 112158923A
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- alumina
- alumina porous
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002242 deionisation method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 5
- 239000011268 mixed slurry Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000010612 desalination reaction Methods 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000013535 sea water Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种可用作电容去离子电极的石墨烯‑氧化铝多孔复合材料的制备方法，通过以多孔氧化铝材料为骨架，以氧化石墨烯分散液和碳酸氢铵或碳酸铵的混合浆料为原料，经真空涂覆后，采用热处理和热还原工艺，制备得到的具有较高比表面积、良好的孔结构和力学强度、以及良好导电性的石墨烯‑氧化铝多孔复合材料，作为电容去离子装置的吸附电极，对溶液中多种价态的离子均具有优良的脱除性能。而且，本发明制备方法具有工艺简单、成本低廉、性能优异、操作条件易控等优点，在海水淡化以及含盐废水处理等领域具有广阔的应用前景。
The invention discloses a preparation method of a graphene-alumina porous composite material which can be used as a capacitive deionization electrode. By using the porous alumina material as a skeleton, a graphene oxide dispersion liquid and ammonium bicarbonate or ammonium carbonate are mixed The slurry is used as a raw material. After vacuum coating, the graphene-alumina porous composite material with high specific surface area, good pore structure and mechanical strength, and good electrical conductivity is prepared by heat treatment and thermal reduction process. The adsorption electrode of the capacitive deionization device has excellent removal performance for ions of various valence states in the solution. Moreover, the preparation method of the present invention has the advantages of simple process, low cost, excellent performance, easy control of operating conditions, etc., and has broad application prospects in the fields of seawater desalination and salt-containing wastewater treatment.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode.
Background
With the increasing global population and the continuous development of industry, the shortage of fresh water resources has become a significant problem facing the world. Desalination of sea water is one of the effective methods to alleviate the above problems. The desalination of sea water and brackish water requires high-efficiency ion removal (desalination) technology, and compared with the traditional desalination technology, the capacitance deionization technology has the outstanding technical advantages of high water resource utilization rate, low energy consumption, easy operation, easy regeneration of electrodes and the like, so that the capacitance deionization technology is paid much attention to the fields of desalination and the like.
Currently, for capacitive deionization technology, the structural performance characteristics of the electrode material are particularly critical to the desalination efficiency. Generally, the electrode material used for capacitive deionization should have the characteristics of good conductivity, large specific surface area, reasonable pore structure and the like. Graphene, as a novel advanced carbon material, has a large theoretical specific surface area (about 2630 m)2The specific surface area of the material is/g), the conductivity is high, and other excellent physical and chemical properties make the material show great application and development prospects in the technical field of capacitive deionization. However, in the current stage of graphene electrode materials, there are, for example: the stacking of sheets is easy to happen, so that the specific surface area of the sheets is reduced, the mechanical strength is low, the technical threshold of regulating and controlling the internal pore structure of the sheets and the preparation cost are high, and the like, thereby being not beneficial to the large-scale popularization and application of the graphene material in the capacitive deionization technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a graphene-alumina porous composite material which has simple process, low cost and easily controlled operation conditions and can be used as a capacitive deionization electrode.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium bicarbonate or ammonium carbonate into graphene oxide dispersion liquid with the concentration of 0.05-0.15 g/L for dissolving to form mixed slurry with the ammonium bicarbonate or ammonium carbonate content of 1-3 wt%;
(2) coating the mixed slurry on the inner and outer surfaces of the porous alumina sheet by adopting a vacuum coating process, then carrying out heat treatment, and repeating coating-heat treatment to obtain the graphene oxide-alumina porous composite material;
(3) and carrying out thermal reduction on the graphene oxide-aluminum oxide porous composite material in a hydrogen atmosphere to obtain the graphene oxide-aluminum oxide porous composite material which can be used as a capacitive deionization electrode.
Furthermore, the particle size of the graphene oxide is 50-200 nm. The most probable pore diameter of the porous alumina sheet is 1-2 mu m, and the porosity is 30-35%.
Further, the processing time of the vacuum coating in the step (2) is 20-30 min; heat treatment is carried out for 2-3 h at the temperature of 95-100 ℃; the number of times of repeating the coating-heat treatment is 5 to 10. The temperature of the thermal reduction treatment in the step (3) is 900-1000 ℃, and the treatment time is 24-36 h. And (4) the resistance of the thermally reduced graphene in the step (3) is 150-200 omega.
The graphene-alumina porous composite material prepared by the invention is subjected to silver screen coating on one surface, two pieces of the graphene-alumina porous composite material are respectively marked as a positive electrode and a negative electrode and are connected with a lead to form the graphene-alumina porous composite electrode, and the graphene-alumina porous composite electrode is suitable for a direct-current power supply with the voltage of 0.6-1.2V.
The invention has the following beneficial effects:
(1) the graphene-alumina porous composite material is prepared by taking a porous alumina material as a framework and taking mixed slurry of graphene oxide dispersion liquid and ammonium bicarbonate or ammonium carbonate as raw materials through a vacuum coating-heat treatment-thermal reduction process, and has a high specific surface area (260-300 m)2The conductive polymer has the advantages of a good pore structure (porosity of 30-35 percent), a good mechanical strength (flexural strength of 23-28 MPa), good conductivity (resistance of 150-200 omega) and low preparation cost, and has excellent effect on ions of multiple valence states in a solution when being used as an adsorption electrode of a capacitive deionization deviceGood removal performance (for Na)+、K+、Ca2+The adsorption rates of (a) are 8 to 35%, 6 to 30%, and 4.5 to 10%, respectively).
(2) The preparation method has the advantages of simple process, low cost, excellent performance, easily controlled operation conditions and the like, and has wide application prospect in the fields of seawater desalination, salt-containing wastewater treatment and the like.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
fig. 1 is a microscopic structural view of a graphene-alumina porous composite material prepared by an example of the present invention;
fig. 2 is a schematic structural diagram of an electrode assembled by the graphene-alumina porous composite material prepared in the embodiment of the present invention.
Detailed Description
The first embodiment is as follows:
the embodiment of the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium carbonate into graphene oxide dispersion liquid with the concentration of 0.05g/L (the particle size of graphene oxide is 50nm) to dissolve the ammonium carbonate to form mixed slurry with the ammonium carbonate content of 1 wt%;
(2) completely immersing a porous alumina sheet with most probable pore diameter of 1 mu m and porosity of 30% into the mixed slurry, treating in-0.9 bar vacuum for 30min to enable graphene oxide and ammonium carbonate to be uniformly combined on the surface of alumina, and then carrying out heat treatment at 100 ℃ for 2h to enable the graphene oxide and the ammonium carbonate to be firmly combined; repeating the coating-heat treatment process for 10 times to obtain a firmly combined graphene oxide-aluminum oxide porous composite material;
(3) the graphene oxide-alumina porous composite material is subjected to thermal reduction treatment after being slowly heated to 1000 ℃ for 36 hours in a hydrogen atmosphere, and the graphene oxide is reduced to graphene with the resistance of 150 omega, so that the graphene oxide-alumina porous composite material capable of being used as a capacitive deionization electrode is obtained.
Example two:
the embodiment of the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium bicarbonate into graphene oxide dispersion liquid with the concentration of 0.15g/L (the particle size of graphene oxide is 200nm) to dissolve the ammonium bicarbonate to form mixed slurry with the ammonium bicarbonate content of 3 wt%;
(2) completely immersing a porous alumina sheet with most probable pore diameter of 2 mu m and porosity of 35% into the mixed slurry, treating in-0.9 bar vacuum for 20min to enable graphene oxide and ammonium bicarbonate to be uniformly combined on the surface of alumina, and then carrying out heat treatment at 95 ℃ for 3h to enable the graphene oxide and the ammonium bicarbonate to be firmly combined; repeating the coating-heat treatment process for 5 times to obtain a firmly combined graphene oxide-aluminum oxide porous composite material;
(3) the graphene oxide-alumina porous composite material is subjected to thermal reduction treatment by slowly heating to 900 ℃ for 24 hours in a hydrogen atmosphere, and the graphene oxide is reduced to graphene with the resistance of 200 omega, so that the graphene oxide-alumina porous composite material capable of being used as a capacitive deionization electrode is obtained.
Example three:
the embodiment of the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium bicarbonate into graphene oxide dispersion liquid with the concentration of 0.10g/L (the particle size of graphene oxide is 100nm) for dissolving to form mixed slurry with the ammonium bicarbonate content of 2 wt%;
(2) completely immersing a porous alumina sheet with most probable pore diameter of 1.5 mu m and porosity of 32% into the mixed slurry, treating in-0.9 bar vacuum for 30min to ensure that the graphene oxide and the ammonium bicarbonate are uniformly combined on the surface of the alumina, and then carrying out heat treatment at 100 ℃ for 2h to ensure that the combination is firm; repeating the coating-heat treatment process for 8 times to obtain a firmly combined graphene oxide-aluminum oxide porous composite material;
(3) the graphene oxide-alumina porous composite material is subjected to thermal reduction treatment by slowly heating to 950 ℃ for 30 hours in a hydrogen atmosphere, and the graphene oxide is reduced to graphene with the resistance of 180 ohms, so that the graphene oxide-alumina porous composite material capable of being used as a capacitive deionization electrode is obtained.
As shown in fig. 1, in the graphene-alumina porous composite material prepared in the embodiment of the present invention, graphene is uniformly coated on the surfaces of all alumina particles. The three-point bending method is adopted to test the flexural strength, and the Archimedes method and the dynamic nitrogen adsorption method are respectively adopted to measure the porosity and the specific surface area, and the test results are shown in Table 1.
Table 1 performance index of graphene-alumina porous composite material prepared in the embodiment of the present invention
As shown in fig. 2, a graphene-alumina porous composite material prepared in the embodiment of the present invention is subjected to silver screen coating on one surface, two sheets are respectively marked as a positive electrode and a negative electrode and connected to a lead to form a graphene-alumina porous composite electrode (i.e., an adsorption electrode), the adsorption electrode is connected to an external power supply with a voltage of 0.6-1.2V, and 100-1000 mg/L NaCl, KCl, CaCl, and CaCl is applied2The solution was subjected to ion adsorption, and the performance index thereof is shown in Table 2.
Table 2 adsorption performance of the graphene-alumina porous composite electrode formed in the example of the present invention
*The solution is NaCl solution, KCl solution, CaCl2And (3) solution.
Claims (6)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023057824A1 (en) * | 2021-10-07 | 2023-04-13 | University Of Colombo | Composition for dye removal from an aqueous system and methods of preparation thereof |
| GB2623155A (en) * | 2022-08-03 | 2024-04-10 | Politechnika Lodzka | A sieve electrode for separating ions |
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| CN103943380A (en) * | 2014-04-24 | 2014-07-23 | 陆艾珍 | Carbon porous electrode preparing method |
| CN105879707A (en) * | 2016-07-03 | 2016-08-24 | 景德镇陶瓷大学 | Reduced-oxidized graphene modified ceramic membrane with efficient ion rejection performance |
| CN107399792A (en) * | 2017-08-16 | 2017-11-28 | 北京理工大学 | A kind of high carrying capacity electric capacity demineralizer for including renewable three-diemsnional electrode |
| CN108117410A (en) * | 2017-12-19 | 2018-06-05 | 华中科技大学 | A kind of three-dimensional porous ceramics-graphene block composite material and preparation method thereof |
| KR102075911B1 (en) * | 2018-10-16 | 2020-02-12 | 한국생산기술연구원 | Composite sensor and manufacturing method thereof |
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- 2020-09-16 CN CN202010974290.5A patent/CN112158923B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN103943380A (en) * | 2014-04-24 | 2014-07-23 | 陆艾珍 | Carbon porous electrode preparing method |
| CN105879707A (en) * | 2016-07-03 | 2016-08-24 | 景德镇陶瓷大学 | Reduced-oxidized graphene modified ceramic membrane with efficient ion rejection performance |
| CN107399792A (en) * | 2017-08-16 | 2017-11-28 | 北京理工大学 | A kind of high carrying capacity electric capacity demineralizer for including renewable three-diemsnional electrode |
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| KR102075911B1 (en) * | 2018-10-16 | 2020-02-12 | 한국생산기술연구원 | Composite sensor and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023057824A1 (en) * | 2021-10-07 | 2023-04-13 | University Of Colombo | Composition for dye removal from an aqueous system and methods of preparation thereof |
| GB2623155A (en) * | 2022-08-03 | 2024-04-10 | Politechnika Lodzka | A sieve electrode for separating ions |
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